Physical Chemistry of Macromolecules

SIAO F. SUN is Professor Emeritus of Chemistry at St. John's University in Jamaica, New York.

• Preface to the Second Edition xvPreface to the First Edition xix1 Introduction 11.1 Colloids 11.2 Macromolecules 31.2.1 Synthetic Polymers 41.2.2 Biological Polymers 71.3 Macromolecular Science 17References 172 Syntheses of Macromolecular Compounds 192.1 Radical Polymerization 192.1.1 Complications 212.1.2 Methods of Free-Radical Polymerization 232.1.3 Some Well-Known Overall Reactions of Addition Polymers 232.2 Ionic Polymerization 252.2.1 Anionic Polymerization 252.2.2 Cationic Polymerization 272.2.3 Living Polymers 272.3 Coordination Polymerization 302.4 Stepwise Polymerization 322.5 Kinetics of the Syntheses of Polymers 332.5.1 Condensation Reactions 342.5.2 Chain Reactions 352.6 Polypeptide Synthesis 402.6.1 Synthesis of Insulin 432.6.2 Synthesis of Ribonucleus 482.7 DNA Synthesis 48References 50Problems 503 Distribution of Molecular Weight 523.1 Review of Mathematical Statistics 533.1.1 Binomial Distribution 533.1.2 Poisson Distribution 543.1.3 Gaussian Distribution 553.2 One-Parameter Equation 563.2.1 Condensation Polymers 573.2.2 Addition Polymers 583.3 Two-Parameter Equations 593.3.1 Normal Distribution 593.3.2 Logarithm Normal Distribution 603.4 Types of Molecular Weight 613.5 Experimental Methods for Determining Molecular Weight and Molecular Weight Distribution 64References 65Problems 654 Macromolecular Thermodynamics 674.1 Review of Thermodynamics 684.2 S of Mixing: Flory Theory 714.3 H of Mixing 754.3.1 Cohesive Energy Density 764.3.2 Contact Energy (First-Neighbor Interaction or Energy Due to Contact) 794.4 G of Mixing 814.5 Partial Molar Quantities 814.5.1 Partial Specific Volume 824.5.2 Chemical Potential 834.6 Thermodynamics of Dilute Polymer Solutions 844.6.1 Vapor Pressure 874.6.2 Phase Equilibrium 89Appendix: Thermodynamics and Critical Phenomena 91References 92Problems 935 Chain Configurations 965.1 Preliminary Descriptions of a Polymer Chain 975.2 Random Walk and the Markov Process 985.2.1 Random Walk 995.2.2 Markov Chain 1015.3 Random-Flight Chains 1035.4 Wormlike Chains 1055.5 Flory’s Mean-Field Theory 1065.6 Perturbation Theory 1075.6.1 First-Order Perturbation Theory 1085.6.2 Cluster Expansion Method 1085.7 Chain Crossover and Chain Entanglement 1095.7.1 Concentration Effect 1095.7.2 Temperature Effect 1145.7.3 Tube Theory (Reptation Theory) 1165.7.4 Images of Individual Polymer Chains 1185.8 Scaling and Universality 119Appendix A Scaling Concepts 120Appendix B Correlation Function 121References 123Problems 1246 Liquid Crystals 1276.1 Mesogens 1286.2 Polymeric Liquid Crystals 1306.2.1 Low-Molecular Weight Liquid Crystals 1316.2.2 Main-Chain Liquid-Crystalline Polymers 1326.2.3 Side-Chain Liquid-Crystalline Polymers 1326.2.4 Segmented-Chain Liquid-Crystalline Polymers 1336.3 Shapes of Mesogens 1336.4 Liquid-Crystal Phases 1346.4.1 Mesophases in General 1346.4.2 Nematic Phase 1356.4.3 Smectic Phase 1356.4.3.1 Smectic A and C 1366.4.4 Compounds Representing Some Mesophases 1366.4.5 Shape and Phase 1376.4.6 Decreasing Order and H of Phase Transition 1386.5 Thermotropic and Lyotropic Liquid Crystals 1386.6 Kerr Effect 1406.7 Theories of Liquid-Crystalline Ordering 1416.7.1 Rigid-Rod Model 1416.7.2 Lattice Model 1426.7.3 De Genne’s Fluctuation Theory 1446.8 Current Industrial Applications of Liquid Crystals 1456.8.1 Liquid Crystals Displays 1466.8.2 Electronic Devices 147References 1497 Rubber Elasticity 1507.1 Rubber and Rubberlike Materials 1507.2 Network Structure 1517.3 Natural Rubber and Synthetic Rubber 1527.4 Thermodynamics of Rubber 1547.5 Statistical Theory of Rubber Elasticity 1587.6 Gels 162References 163Problems 1648 Viscosity and Viscoelasticity 1658.1 Viscosity 1658.1.1 Capillary Viscometers 1668.1.2 Intrinsic Viscosity 1708.1.3 Treatment of Intrinsic Viscosity Data 1728.1.4 Stokes’ Law 1768.1.5 Theories in Relation to Intrinsic Viscosity of Flexible Chains 1768.1.6 Chain Entanglement 1798.1.7 Biological Polymers (Rigid Polymers Inflexible Chains) 1818.2 Viscoelasticity 1848.2.1 Rouse Theory 1878.2.2 Zimm Theory 190References 192Problems 1939 Osmotic Pressure 1989.1 Osmometers 1999.2 Determination of Molecular Weight and Second Virial Coefficient 1999.3 Theories of Osmotic Pressure and Osmotic Second Virial Coefficient 2029.3.1 McMillan–Mayer Theory 2039.3.2 Flory Theory 2049.3.3 Flory–Krigbaum Theory 2059.3.4 Kurata–Yamakawa Theory 2079.3.5 des Cloizeaux–de Gennes Scaling Theory 2099.3.6 Scatchard’s Equation for Macro Ions 213Appendix A Ensembles 215Appendix B Partition Functions 215Appendix C Mean-Field Theory and Renormalization Group Theory 216Appendix D Lagrangian Theory 217Appendix E Green’s Function 217References 218Problems 21810 Diffusion 22310.1 Translational Diffusion 22310.1.1 Fick’s First and Second Laws 22310.1.2 Solution to Continuity Equation 22410.2 Physical Interpretation of Diffusion: Einstein’s Equation of Diffusion 22610.3 Size Shape and Molecular Weight Determinations 22910.3.1 Size 22910.3.2 Shape 23010.3.3 Molecular Weight 23110.4 Concentration Dependence of Diffusion Coefficient 23110.5 Scaling Relation for Translational Diffusion Coefficient 23310.6 Measurements of Translational Diffusion Coefficient 23410.6.1 Measurement Based on Fick’s First Law 23410.6.2 Measurement Based on Fick’s Second Law 23510.7 Rotational Diffusion 23710.7.1 Flow Birefringence 23910.7.2 Fluorescence Depolarization 239References 240Problems 24011 Sedimentation 24311.1 Apparatus 24411.2 Sedimentation Velocity 24611.2.1 Measurement of Sedimentation Coefficients: Moving-Boundary Method 24611.2.2 Svedberg Equation 24911.2.3 Application of Sedimentation Coefficient 24911.3 Sedimentation Equilibrium 25011.3.1 Archibald Method 25111.3.2 Van Holde–Baldwin (Low-Speed) Method 25411.3.3 Yphantis (High-Speed) Method 25611.3.4 Absorption System 25811.4 Density Gradient Sedimentation Equilibrium 25911.5 Scaling Theory 260References 262Problems 26312 Optical Rotatory Dispersion and Circular Dichroism 26712.1 Polarized Light 26712.2 Optical Rotatory Dispersion 26712.3 Circular Dichroism 27212.4 Cotton Effect 27512.5 Correlation Between ORD and CD 27712.6 Comparison of ORD and CD 280References 281Problems 28113 High-Performance Liquid Chromatography and Electrophoresis 28413.1 High-Performance Liquid Chromatography 28413.1.1 Chromatographic Terms and Parameters 28413.1.2 Theory of Chromatography 28913.1.3 Types of HPLC 29113.2 Electrophoresis 30013.2.1 Basic Theory 30013.2.2 General Techniques of Modern Electrophoresis 30513.2.3 Agarose Gel Electrophoresis and Polyacrylamide Gel Electrophoresis 30713.2.4 Southern Blot Northern Blot and Western Blot 30913.2.5 Sequencing DNA Fragments 31013.2.6 Isoelectric Focusing and Isotachophoresis 31013.3 Field-Flow Fractionation 314References 317Problems 31814 Light Scattering 32014.1 Rayleigh Scattering 32014.2 Fluctuation Theory (Debye) 32414.3 Determination of Molecular Weight and Molecular Interaction 32914.3.1 Two-Component Systems 32914.3.2 Multicomponent Systems 32914.3.3 Copolymers 33114.3.4 Correction of Anisotropy and Deporalization of Scattered Light 33314.4 Internal Interference 33314.5 Determination of Molecular Weight and Radius of Gyration of the Zimm Plot 337Appendix Experimental Techniques of the Zimm Plot 341References 345Problems 34615 Fourier Series 34815.1 Preliminaries 34815.2 Fourier Series 35015.2.1 Basic Fourier Series 35015.2.2 Fourier Sine Series 35215.2.3 Fourier Cosine Series 35215.2.4 Complex Fourier Series 35315.2.5 Other Forms of Fourier Series 35315.3 Conversion of Infinite Series into Integrals 35415.4 Fourier Integrals 35415.5 Fourier Transforms 35615.5.1 Fourier Transform Pairs 35615.6 Convolution 35915.6.1 Definition 35915.6.2 Convolution Theorem 36115.6.3 Convolution and Fourier Theory: Power Theorem 36115.7 Extension of Fourier Series and Fourier Transform 36215.7.1 Lorentz Line Shape 36215.7.2 Correlation Function 36315.8 Discrete Fourier Transform 36415.8.1 Discrete and Inverse Discrete Fourier Transform 36415.8.2 Application of DFT 36515.8.3 Fast Fourier Transform 366Appendix 367References 368Problems 36916 Small-Angle X-Ray Scattering Neutron Scattering and Laser Light Scattering 37116.1 Small-Angle X-ray Scattering 37116.1.1 Apparatus 37216.1.2 Guinier Plot 37316.1.3 Correlation Function 37516.1.4 On Size and Shape of Proteins 37716.2 Small-Angle Neutron Scattering 38116.2.1 Six Types of Neutron Scattering 38116.2.2 Theory 38216.2.3 Dynamics of a Polymer Solution 38316.2.4 Coherently Elastic Neutron Scattering 38416.2.5 Comparison of Small-Angle Neutron Scattering with Light Scattering 38416.2.6 Contrast Factor 38616.2.7 Lorentzian Shape 38816.2.8 Neutron Spectroscopy 38816.3 Laser Light Scattering 38916.3.1 Laser Light-Scattering Experiment 38916.3.2 Autocorrelation and Power Spectrum 39016.3.3 Measurement of Diffusion Coefficient in General 39116.3.4 Application to Study of Polymers in Semidilute Solutions 39316.3.4.1 Measurement of Lag Times 39316.3.4.2 Forced Rayleigh Scattering 39416.3.4.3 Linewidth Analysis 394References 395Problems 39617 Electronic and Infrared Spectroscopy 39917.1 Ultraviolet (and Visible) Absorption Spectra 40017.1.1 Lambert–Beer Law 40217.1.2 Terminology 40317.1.3 Synthetic Polymers 40517.1.4 Proteins 40617.1.5 Nucleic Acids 40917.2 Fluorescence Spectroscopy 41217.2.1 Fluorescence Phenomena 41217.2.2 Emission and Excitation Spectra 41317.2.3 Quenching 41317.2.4 Energy Transfer 41617.2.5 Polarization and Depolarization 41817.3 Infrared Spectroscopy 42017.3.1 Basic Theory 42017.3.2 Absorption Bands: Stretching and Bending 42117.3.3 Infrared Spectroscopy of Synthetic Polymers 42417.3.4 Biological Polymers 42717.3.5 Fourier Transform Infrared Spectroscopy 428References 430Problems 43218 Protein Molecules 43618.1 Protein Sequence and Structure 43618.1.1 Sequence 43618.1.2 Secondary Structure 43718.1.2.1 a-Helix and b-Sheet 43718.1.2.2 Classification of Proteins 43918.1.2.3 Torsion Angles 44018.1.3 Tertiary Structure 44118.1.4 Quarternary Structure 44118.2 Protein Structure Representations 44118.2.1 Representation Symbols 44118.2.2 Representations of Whole Molecule 44218.3 Protein Folding and Refolding 44418.3.1 Computer Simulation 44518.3.2 Homolog Modeling 44718.3.3 De Novo Prediction 44718.4 Protein Misfolding 44818.4.1 Biological Factor: Chaperones 44818.4.2 Chemical Factor: Intra- and Intermolecular Interactions 44918.4.3 Brain Diseases 45018.5 Genomics Proteomics and Bioinformatics 45118.6 Ribosomes: Site and Function of Protein Synthesis 452References 45419 Nuclear Magnetic Resonance 45519.1 General Principles 45519.1.1 Magnetic Field and Magnetic Moment 45519.1.2 Magnetic Properties of Nuclei 45619.1.3 Resonance 45819.1.4 Nuclear Magnetic Resonance 46019.2 Chemical Shift (d) and Spin–Spin Coupling Constant (J) 46119.3 Relaxation Processes 46619.3.1 Spin–Lattice Relaxation and Spin–Spin Relaxation 46719.3.2 Nuclear Quadrupole Relaxation and Overhauser Effect 46919.4 NMR Spectroscopy 47019.4.1 Pulse Fourier Transform Method 47119.4.1.1 Rotating Frame of Reference 47119.4.1.2 The 90 Pulse 47119.4.2 One-Dimensional NMR 47219.4.3 Two-Dimensional NMR 47319.5 Magnetic Resonance Imaging 47519.6 NMR Spectra of Macromolecules 47719.6.1 Poly(methyl methacrylate) 47719.6.2 Polypropylene 48119.6.3 Deuterium NMR Spectra of Chain Mobility in Polyethylene 48219.6.4 Two-Dimensional NMR Spectra of Poly-g-benzyl-L-glutamate 48519.7 Advances in NMR Since 1994 48719.7.1 Apparatus 48719.7.2 Techniques 48719.7.2.1 Computer-Aided Experiments 48719.7.2.2 Modeling of Chemical Shift 48819.7.2.3 Protein Structure Determination 48919.7.2.4 Increasing Molecular Weight of Proteins for NMR study 49119.8 Two Examples of Protein NMR 49119.8.1 A Membrane Protein 49319.8.2 A Brain Protein: Prion 494References 494Problems 49520 X-Ray Crystallography 49720.1 X-Ray Diffraction 49720.2 Crystals 49820.2.1 Miller Indices, hkl 49820.2.2 Unit Cells or Crystal Systems 50220.2.3 Crystal Drawing 50320.3 Symmetry in Crystals 50420.3.1 Bravais Lattices 50520.3.2 Point Group and Space Group 50620.3.2.1 Point Groups 50720.3.2.2 Interpretation of Stereogram 50920.3.2.3 Space Groups 51220.4 Fourier Synthesis 51520.4.1 Atomic Scattering Factor 51520.4.2 Structure Factor 51520.4.3 Fourier Synthesis of Electron Density 51620.5 Phase Problem 51720.5.1 Patterson Synthesis 51720.5.2 Direct Method (Karle–Hauptmann Approach) 51820.6 Refinement 51920.7 Crystal Structure of Macromolecules 52020.7.1 Synthetic Polymers 52020.7.2 Proteins 52320.7.3 DNA 52320.8 Advances in X-Ray Crystallography Since 1994 52520.8.1 X-Ray Sources 52520.8.2 New Instruments 52620.8.3 Structures of Proteins 52620.8.3.1 Comparison of X-Ray Crystallography with NMR Spectroscopy 52720.8.4 Protein Examples: Polymerse and Anthrax 528Appendix Neutron Diffraction 530References 532Problems 533Author Index 535Subject Index 543

"...a useful addition to the libraries of scientists, researchers, and engineers working in this field...could also serve as an undergraduate text in a polymers or chemistry program." (Materials and Manufacturing Processes, August 2006) "...a modern overview of polymer physical chemistry...a valuable addition to any polymer scientist's library, and it is hard to imagine anyone not getting a lot of useful information and inspiration from reading it." (Polymer News)